Search Results (22)

This paper concerns interactive Monte Carlo simulations for adiabatic ensembles and a genetic algorithm to research and educational contexts. In the Introduction, we discuss some concepts of thermodynamics, statistical mechanics and ensembles relevant to molecular simulations. The second and third sections of the paper comprise two programs in JavaScript regarding (i) argon in the grand-isobaric ensemble focusing on the direct calculation of entropy, vapor–liquid equilibria and radial distribution functions and (ii) an ideal system of quantized harmonic oscillators in the microcanonical ensemble for the determination of the entropy and Boltzmann distribution, also including the definition of Boltzmann and Gibbs entropies relative to classical systems. The fourth section is concerned with a genetic algorithm program in Java, as a pedagogical alternative to introduce the Second Law of Thermodynamics, which summarizes artificial intelligence methods and the cumulative selection process in biogenesis. Full article

A solubility model of SO₂ in multi-ion electrolyte solutions has been developed by the activity-fugacity relation at vapor-liquid equilibria. The fugacity coefficient of SO₂ in the vapor phase is calculated by the equation of state (EOS) of pure SO₂, and the activity coefficient of SO₂ in the liquid phase is calculated by the Pitzer activity coefficient theory. The model can reproduce the reliable solubility data of SO₂ in pure water and multi-ion electrolyte solutions (Na⁺, K⁺, Cl⁻, ${\mathrm{SO}}_4^{2-}$) within or close to experimental uncertainties. Although the second-order and third-order interaction parameters between SO₂ and Mg²⁺ and Ca²⁺ have been adopted by an approximation, the solubility model can also be extended to predict the SO₂ solubility in seawater. In addition, combining with the EOS of a CO₂-SO₂ fluid mixture, the model can be used to predict the solubility of a CO₂-SO₂ mixture in aqueous electrolyte solutions. The calculated results are consistent with experimental data, which indicates that the solubility model has certain predictive ability. Full article

As global environmental consciousness continues to expand, the issue of refrigerant alternatives has increasingly become a focal point for scholarly attention. Using CiteSpace visualization technology, a comprehensive and innovative research framework for refrigerant alternatives has been developed. This framework systematically organizes and analyzes not only the volume of publications related to refrigerant alternatives but also the collaborative relationships among authors and research institutions. By employing keyword co-occurrence maps, clustering diagrams, and timeline charts, an in-depth analysis of the academic literature on refrigerant alternatives has been performed, elucidating the core research themes, evolutionary trajectories, and emerging trends in this field. Research indicates an exponential increase in the number of studies on refrigerant alternatives; however, there is insufficient collaboration and communication among researchers and institutions. Key research hotspots in this field encompass the organic Rankine cycle, vapor-liquid equilibria, pressure drop characteristics, vapor compression refrigeration systems, exergy analysis, alternative refrigerants, and performance evaluation of carbon dioxide systems. In future research, the performance of various low GWP refrigerants in refrigeration cycle systems will continue to be a focal point. To address diverse application requirements, developing blended refrigerants represents a pragmatic technical approach. From a sustainability standpoint, natural refrigerants are anticipated to emerge as the ultimate alternative, with the technical challenges associated with their application constituting a critical area for future investigation. Full article

The growing demand for more sustainable routes and processes in the mixture separation and purification industry has generated a need to search for innovations, with new solvent alternatives being a possible solution. In this context, a new class of green solvents, known as deep eutectic solvents (DESs), has been gaining prominence in recent years in both academic and industrial spheres. These solvents, when compared to ionic liquids (ILs), are more environmentally friendly, less toxic, low-cost, and easier to synthesize. In addition, they have significantly lower melting points than their precursors, offering a promising option for various applications in this industrial sector. Understanding and studying the thermodynamic behavior of systems composed of these substances in purification and separation processes, such as liquid–liquid extraction and azeotropic distillation, is extremely important. This work aimed to study the phase behavior of liquid–liquid equilibrium (LLE) and vapor–liquid equilibrium (VLE) of water + 1-butanol + DES (choline chloride + glycerol) systems with a molar ratio of 1:2. Experimental LLE data, obtained at 298.15 K and 101.3 kPa, and VLE data, obtained at 101.3 kPa and in the temperature range of 364.05 K–373.85 K, were submitted to the thermodynamic quality/consistency test, proposed by Marcilla et al. and Wisniak, and subsequently modeled using the gamma–gamma approach for the LLE and gamma–phi for the VLE. The non-random two-liquid (NRTL) model was used to calculate the activity coefficient. The results are presented for the VLE in a temperature–composition phase diagram (triangular prism) and triangular phase diagrams showing the binodal curve and tie lines (LLE). The separation and distribution coefficients of LLE were determined to evaluate the extractive potential of the DES. For the VLE, the values of the relative volatility of the system were calculated, considering the entrainer free-basis, to evaluate the presence or absence of azeotropes in the range of collected points. From these data, it was possible to compare DES with ILs as extracting agents, using data from previous studies carried out by the research group. Therefore, the results indicate that the NRTL model is efficient at correlating the fluid behavior of both equilibria. Thus, this study serves as a basis for future studies related to the understanding and design of separation processes. Full article

Vapor pressures and other thermodynamic properties of liquids, such as density and enthalpy of mixtures, are the key parameters in chemical engineering for designing new process units, and are also essential for understanding the physical chemistry, macroscopic and molecular behavior of fluid systems. In this work, vapor pressures between 278.15 and 323.15 K, densities and enthalpies of mixtures between 288.15 and 318.15 K for the binary mixture (2-propanol + 1,8-cineole) have been measured. From the vapor pressure data, activity coefficients and excess Gibbs energies were calculated via the Barker’s method and the Wilson equation. Excess molar volumes and excess molar enthalpies were also obtained from the density and calorimetric measurements. Thermodynamic consistency test between excess molar Gibbs energies and excess molar enthalpies has been carried out using the Gibbs–Helmholtz equation. Robinson–Mathias, and Peng–Robinson–Stryjek–Vera together with volume translation of Peneloux equations of state (EoS) are considered, as well as the statistical associating fluid theory that offers a molecular vision quite suitable for systems having highly non-spherical or associated molecules. Of these three models, the first two fit the experimental vapor pressure results quite adequately; in contrast, only the last one approaches the volumetric behavior of the system. A brief comparison of the thermodynamic excess molar functions for binary mixtures of short-chain alcohol + 1,8-cineole (cyclic ether), or +di-n-propylether (lineal ether) is also included. Full article

A new element- and chemical bond-dependent G^E-EoS model(SRK-UNICAC) is proposed to consider the deviation of the vapor and liquid phases from the ideal state. The SRK-UNICAC model combines the UNICAC model and the SRK cubic equation of state. It uses the original interaction parameters of the UNICAC model and uses this model to calculate the G^E. The SRK-UNICAC model predicted vapor-liquid equilibria for 87 binary systems under low- and medium-pressure conditions, 12 binary systems under high-pressure conditions, and 14 ternary systems; a comparison of the predictions with five other activity coefficient models were also made. The new model predicted the vapor-phase fraction and bubble-point pressure, and temperature for the binary system at high pressure, with a mean relative error of 3.75% and 6.58%, respectively. The mean relative errors of vapor-phase fraction and bubble-point temperature or bubble-point pressure for ternary vapor–liquid phase equilibrium were 6.50%, 4.76%, and 2.25%. The SRK-UNICAC model is more accurate in predicting the vapor–liquid phase equilibrium of high-pressure, non-polar, and polar mixtures and has a simpler and wider range of prediction processes. It can therefore be applied to the prediction of vapor–liquid equilibrium. Full article

The comprehensive topological isomorphism of liquid–vapor, fusibility, and solubility diagrams in the proper sets of variables is proven with the aid of van der Waals equations of the shift in phase equilibrium. Analogues of Gibbs–Konovalov and Gibbs–Roozeboom laws are demonstrated in solubility diagrams of ternary and quaternary systems under crystallization of different types of solid solutions. For the demonstration, the quaternary reciprocal system ${\mathrm{K}}^{+},{\mathrm{NH}}_4^{+}\left|\right|{\mathrm{Cl}}^{-},{\mathrm{Br}}^{-}-{\mathrm{H}}_2\mathrm{O}$ and its ternary subsystems with modeling of the liquid phase within the framework of the classical Pitzer formalism are mainly used. An algorithm for calculating solubility equilibria in these systems is given. Full article

Tools to predict vapor–liquid phase equilibria are indispensable for the conceptualization and design of separation processes. Modified separation of cohesive energy density (MOSCED) is a solubility-parameter-based method parameterized to make accurate predictions of the limiting activity coefficient. As a solubility-parameter-based method, MOSCED can not only make quantitative predictions, but can shed light on the underlying intermolecular interactions. In the present study, we demonstrated the ability of MOSCED to correlate the enthalpy of vaporization and vapor pressure at a specific temperature using multiple linear regression. With this addition, MOSCED is able to predict vapor–liquid phase equilibria in the absence of reference data. This was demonstrated for the prediction of the Henry’s constant and solvation free energy of organic solutes in water, which was found to be superior to mod-UNIFAC. In addition to being able to make phase equilibrium predictions, the ability to correlate the enthalpy of vaporization and vapor pressure offers the opportunity to include additional properties in the regression of the MOSCED parameters. Given this success, we additionally attempted to correlate a wide range of physical properties using a similar expression. While, in some cases, the results were reasonable, they were inferior to the correlations of the enthalpy of vaporization and vapor pressure. Future efforts will be needed to improve the correlations. Full article

In the current research, the binary solution containing ionic liquid (IL), 1-ethyl-1-methylmorpholinium dimethyl phosphate ([C₁C₂MOR][DMP]), 1-ethyl-1-methylpiperidinium dimethyl phosphate ([C₁C₂PIP][DMP]), or N,N,N-triethyl-N-methylammonium dimethyl phosphate ([N_1,2,2,2][DMP]) with ethanol are investigated as new working fluids for absorption refrigeration technology. The IL was mixed with ethanol, which was considered as a refrigerant. Experimental (vapor + liquid) phase equilibria (VLE) of these binary systems were measured by an ebulliometric method within a temperature range from T = (328.15 to 348.15) K with an increment of 10 K and pressures up to 90 kPa. Experimental VLE data were correlated using non-random two-liquid (NRTL) within the maximum average relative deviation of 0.45%, which confirms the effectiveness of using such a model for calculations. Each of the proposed binary systems exhibit a negative deviation from Raoult’s law, which is a very important characteristic for working pairs used in absorption heat pumps or absorption refrigerators. From a technological point of view, measurements of physicochemical properties play an important role. In this research, liquid density and dynamic viscosity were determined at temperatures from T = (293.15 to 338.15) K at ambient pressure over the whole concentration range. These properties were correlated using empirical equations. From experimental density data, the excess molar volumes were determined and correlated using the Redlich–Kister type equation. Ionic liquid: [C₁C₂MOR][DMP] and [C₁C₂PIP][DMP] were synthesized and characterized using NMR analysis. The thermophysical characterization of pure ILs, including glass transition temperature (T_g) and heat capacity at the glass transition temperature (Δ_gC_p), was determined using the differential scanning calorimetry technique (DSC) at atmospheric pressure. In this work, the combination of basic studies on the effect of the cation structure of an ionic liquid on the properties of their solutions with ethanol and the possibility of future application of the tested systems in a viable refrigeration system are presented. Full article

In this work, an algorithm was developed to determine different possibilities of distillation cuts to support productivity and improve the final quality of cachaça, a Brazilian spirit beverage. The distillation process was simulated using the Aspen Plus^® software, considering a wide range of fermented musts compositions available in the literature obtained by fermentation with different yeast strains. Twenty-four simulations were carried out considering eight compounds as follows: water and ethanol (major compounds); acetic acid, acetaldehyde, ethyl acetate, 1-propanol, isobutanol, and isoamyl alcohol (minor compounds). The calculations considered a long-time process, i.e., until almost all the ethanol in the fermented must was distilled. The algorithm enabled the identification of countless distilling cuts, resulting in products with different alcoholic grades and process yields. One fermented must became viable to produce cachaça after the suggested non-traditional method of cuts proposed in this work. Furthermore, the non-traditional distilling cut provided a productivity gain of more than 50%. Finally, the ratio of acetaldehyde and ethanol concentration was the key parameter to determine whether the fermented musts could provide products meeting cachaça’s legislation. Full article

In the Supercritical Antisolvent process (SAS), the thermodynamic behavior of complex multicomponent systems can influence the particles’ morphology. However, due to the limited thermodynamic data for multicomponent systems, the effect of solutes is often neglected, and the system is considered as pseudo-binary. It has been demonstrated that the presence of a solute can significantly influence the thermodynamic behavior of the system. In particular, when the SAS process is adopted for the production of drug/polymer coprecipitated microparticles, the effect of both the drug and the polymer in the solvent/CO₂ mixture should be considered. In this work, the effect of polyvinylpyrrolidone (PVP), used as the carrier, and of the liposoluble vitamins menadione (MEN) and α-tocopherol (TOC), as model drugs, was investigated as a deviation from the fundamental thermodynamic behavior of the DMSO/CO₂ binary system. Vapor–liquid equilibria (VLE) were evaluated at 313 K, with a PVP concentration in the organic solution equal to 20 mg/mL. The effect of the presence of PVP, MEN, and TOC on DMSO/CO₂ VLE at 313 K was studied; furthermore, the effect of PVP/MEN and PVP/TOC, at a polymer/drug ratio of 5/1 and 3/1, was determined. Moreover, SAS precipitation experiments were performed at the same polymer/drug ratios using a pressure of 90 bar. Thermodynamic studies revealed significant changes in phase behavior for DMSO/CO₂/PVP/TOC and DMSO/CO₂/PVP/MEN systems compared to the binary DMSO/CO₂ system. From the analysis of the effect of the presence of a single compound on the binary system VLE, it was noted that PVP slightly affected the thermodynamic behavior of the system. In contrast, these effects were more evident for the DMSO/CO₂/TOC and DMSO/CO₂/MEN systems. SAS precipitation experiments produced PVP/MEN and PVP/TOC microparticles, and the obtained morphology was justified considering the quaternary systems VLE. Full article

It is extremely dangerous for a turbocharged boiler to have a leakage fault in its vaporization tube. However, early detection and fault diagnosis of micro-leakage faults are very difficult. On the one hand, there are few fault samples that lead to a difficult and intelligent diagnosis. On the other hand, the system fault response characteristics of the characterization parameters in the process are complex and easily confused with the load-changing characteristics. In order to obtain fault samples and identify fault characteristics, a fault simulation model for the micro-leakage of the boiler evaporation tube is established based on the dynamic mathematical model of all working conditions. The model’s effectiveness is verified by typical fault experiments. The dynamic simulation experiments of three kinds of micro-leakage and four kinds of load changing were carried out. Through the analysis of combustion equilibrium and vapor-liquid equilibrium of 14 groups of characterization parameters, it is found that: (1) The reason for the poor discriminability in micro-leakage faults is that most of the characterization parameters tend to balance after 300 s and the dynamic response characteristics are similar to those of load increase. (2) There are four highly distinguishable parameters: the speed of the turbocharger unit, the air supply flow, the flue gas temperature at the superheater outlet, and the furnace pressure. When the micro-leakage fault is triggered, the first three parameters have a large disturbance. They show a trend of decreasing first and then increasing in short periods, unlike normal load-changing conditions. The fourth parameter (furnace pressure) rises abnormally fast after failure. (3) Under the normal working condition of varying loads, the main common parameters take 300 s to stabilize; the common stability parameter values should be recorded because when the micro-leakage fault of evaporation occurs, the steady-state increment of failure is larger than the normal steady increment under variable load conditions, by 2 to 3 times. (4) As the leakage fault increases, the disturbance amplitude of the characteristic parameters becomes larger. In addition, the stability of the steam system becomes worse, and fault discrimination becomes more obvious. Full article

This work attempts to address the quest of removing carbon dioxide from flue gas streams to help preserve the environment. It is based on a model that is able to describe the solid-liquid-vapour and solid-vapour phase equilibria for the ternary system of N₂-O₂-CO₂ at pressures from 5 to 130 bar and over a wide range of temperature (140 to 220 K). Furthermore, a corresponding state-of-the art solid-vapor (SV) CO₂ capture/separation unit is developed and introduced in this work. The SV unit was modeled using the Aspen Custom Modeler software by implementing the thermodynamic model developed before. It was then simulated using the Aspen Plus simulator; its performance was studied and analyzed. Moreover, the performance of the unit was optimized and compared to the most conventional corresponding technology used by the industry (i.e., amine-scrubbing). Results proved that for the same output clean gas composition, which contains only 0.3% CO₂, the developed state-of-the-art SV unit consumes almost half of the energy required by the conventional process. Other advantages of the novel SV separation unit include the lower requirement of capital equipment, no need of additional agents (such as solvents) and the avoidance of product contamination with such additional agents. Full article

Molecular dynamics simulations of ultrathin free-standing layers made of melted (373.15–673.15 K) polyethylene chains, which exhibit a lower melting temperature (compared to the bulk value), were carried out to investigate the dominant pressure forces that shape the conformation of chains at the interfacial and bulk liquid regions. We investigated layer thicknesses, $t_L$, from the critical limit of mechanical stability up to lengths of tens of nm and found a normal distribution of bonds dominated by slightly stretched chains across the entire layer, even at large temperatures. In the bulk region, the contribution of bond vibrations to pressure was one order of magnitude larger than the contributions from interchain interactions, which changed from cohesive to noncohesive at larger temperatures just at a transition temperature that was found to be close to the experimentally derived onset temperature for thermal stability. The interchain interactions produced noncohesive interfacial regions at all temperatures in both directions (normal and lateral to the surface layer). Predictions for the value of the surface tension, $\gamma$, were consistent with experimental results and were independent of $t_L$. However, the real interfacial thickness—measured from the outermost part of the interface up to the point where $\gamma$ reached its maximum value—was found to be dependent on $t_L$, located at a distance of 62 Å from the Gibbs dividing surface in the largest layer studied (1568 chains or 313,600 bins); this was ~4 times the length of the interfacial thickness measured in the density profiles. Full article

The CPA equation of state is applied to model binary, ternary, and multicomponent mixtures that contain CO₂ with polyethylene glycols or compounds relevant to biodiesel production, such as glycerol and various triglycerides. Effort has been made to evaluate the model performance on correlating both the liquid and the vapor phase compositions, which is a demanding task, revealing the model’s and parameters’ limitations, due to the rather low concentrations of heavy compounds in the vapor phase. Initially the model’s binary parameters, which in all cases were temperature independent, were estimated using experimental data for binary systems. Those parameters were used to predict the phase behavior of supercritical CO₂ containing ternary and multicomponent mixtures. Since no parameter was adjusted to ternary or multicomponent systems’ data, the reported CPA results for such mixtures are considered as pure predictions. This is the final part of a series of studies [Tsivintzelis et al. Fluid Phase Equilibria 430 (2016) 75–92 and 504 (2020) 112337] that complete the parameterization of the CPA equation of state for systems relevant to the biodiesel production, which allows the application of the model to multicomponent mixtures of the relevant processes. Full article